ON THE APPLICATIONS OF GRIGNARD’S REACTION. 281 
Methane, for example, is evolved by the addition of water to magnesium 
methyl iodide ; 
CH,Mgl + H,0 = CH, + MgIOH 
An alcohol has the same effect as water; for example :— 
CH,Mgl + C,H,OH = CH, + 00,4, . MgI 
Indeed, any compound containing a hydroxyl group behaves in this 
manner, this property of hydroxylic compounds having been recom- 
mended both as a means for their qualitative detection and for sepa- 
rating them from compounds which do not interact with the Grignard 
reagent.! A method for the estimation of hydroxyl groups in carbon 
compounds is based by Hibbert and Sudborough ? on this reaction, where, 
however, amyl ether is substituted for ethyl ether in the preparation of 
the reagent. Zerewitinoff* claims the method to be suitable for esti- 
mating the number of hydroxyl groups in a carbon compound. 
Allelotropic compounds generally act on the Grignard reagent in 
accordance with the hydroxylic structure, thus /-menthylacetoacetate 
reacts in accordance with the formula CH,.C(OH): CH.COOC,,H,, 
and not as CH,.CO.CH,. COOC,)H)j5.4 
A regular current of methane is evolved by the addition of dry 
powdered ammonium chloride to magnesium methyl iodide :— ° 
2CH,Mgl + NH,Cl = 2CH, + NH, . MgI + MgICl 
When a current of dry ammonia is passed into an ethereal solution of 
magnesium ethyl iodide, ethane is evolved ;-— 
C,H,Mgl + NH, = C,H,+NH,. MgI 
Primary or secondary amines exhibit a similar behaviour ; thus with 
aniline and methyl aniline :— 
C,H,MgI + C,H, . NH, =C,H,+C,H,.NH. Mgl 
C,H,Mgl + C,H, .NHCH, = C,H, + C,H,N(CH,) . Mgl ° 
The action of a primary amine is possibly, however, more complex than 
this representation of Meunier, since Houben’ concludes that the action 
2CH,Mel + C,H,NH, = C,H,NH . MgI,CH,Mgl + CH, 
takes place in the cold if the proportions of magnesium methyl iodide and 
aniline, indicated by the equation given, are used. If, however, a second 
molecular proportion of aniline is added to the hot solution, methane jis 
again evolved, thus :—’ 
C,H, . NH. MgI,CH,MgI + C,H,NH,=2C,H, .NHMgI +CH, 
A method for making aromatic hydrocarbons has been devised by 
Werner and Zilkens,* who use methyl] sulphate ; thus p-xylene in a 75 per 
cent. yield is obtained from magnesium p-tolyl bromide :— 
CH, .C,H,. MgBr + (CH,),SO, = C,H,(CH,), + CH, .SO,. MgBr 
1 I'schugaeff, Ber., 1902, 35, 3912. 2 Trans. Chem. Soc., 1904, 85, 933. 
3 Ber., 1907, 40, 2023. 
4 McKenzie, Trans. Chem. Soc., 1906, &9, 380. 
5 Houben, Ber., 1905, 38, 3017. 
6 Meunier, Compt. rend., 1903, 186, 758; Bull. Soc. Chim., 1903, 29, 314. 
7 Houben, Ber., 1905, 38, 3017. Compare Sudborough and Hibbert, Proc. Chem, 
Soc., 1904, 20, 165. 
® Ber., 1908, 36, 2116, 3618, Compare Houben, idid., 3083, 
